Silver halide color photographic material

ABSTRACT

A multi-layered photographic material comprising a support and (a) blue-sensitive, (b) green-sensitive, and (c) red-sensitive emulsion layers on said support, these layers containing colorless and diffusion-resistant couplers forming yellow, magenta, and cyan respectively upon coupling, wherein at least one of the layers contains a combination of two couplers differing in coupling activity rate by at least 1.5 times from each other and giving two dyes of the same absorption area, that is, 400 to 500 m Mu for (a), 500 to 600 m Mu for (b), and 600 to 700 m Mu for (c). Especially preferred couplers are acylacetanilides for (a), 5-pyrazolones, indazolones and pyrazolobenzimidazoles for (b), and phenols and Alpha -naphthols for (c). The specific combination of couplers contributes to the widening of the color gamut of the color photographic material.

United States Patent 191 Ohta et al.

451 May 21, 1974 [75] Inventors: Noboru Ohta; Yasushi Oishi; Hirozo Ueda, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Company, Ltd.,

Kanagawa, Japan [22] Filed: Dec. 8, 1971 [21 Appl. No.: 206,060

{3 0] Foreign Application Priority Data Dec. 8, 1970 Japan 45-10843 8 [52] us. c1. 96/74, 96/22 [51] Int. Cl. G03c l/76, G03c 3/00,,G03c 7/16 I [58] -'Field of Search; 96/74, 100, 22

i [56] References Cited UNITED STATES PATENTS 3,415,652 12/1968 Porter 96/74 3,419,391 12/1968 Young 96/74 3,468,665 9/1969 Misu 96/74, 3,476,563 11/1969 Loria 96/74 3,515,557 6/197O Chu 96/74 3,516,831 6/1970 Wolf. 96/74 3,640,716 2/1972 Nagae 96/74 FOREIGN PATENTS OR APPLICATIONS 533,069 11/1956 Canada 96/74 923,045 4/1963 Great Britain 96/74 Primary ExaminerNorman G. Torchin Assistant Examiner-Richard L. Schilling Attorney, Agent, or Firm-Sughrue, Rothwe'll, Mion, Zinn & Macpeak [57] ABSTRACT A multi-layered photographic material comprising a support and (a) blue-sensitive, (b) green-sensitive, and (c) red-sensitive emulsion layers on said support, these layers containing colorless and diffusionresistant couplers forming yellow, magenta, and cyan respectively upon coupling, wherein at least one of the layers contains a combination of two couplers differing in coupling activity rate by at least 1.5 times from each other and giving two dyes of the same absorption area, that is, 400 to 500 mp. for (a), 500 to 600 mp. for (b), and 600 to 700 my. for (0). Especially preferred couplers are acylacetanilides for (a), 5- pyrazolones, indazolones and pyrazolobenzimidazoles for (b), and phenols and a-naphthols for (c). The specific combination of couplers contributes to the widening of the color gamut of the color photographic material.

12 Claims, 5 Drawing Figures I PATENTEUIIAYZI m4 Mill-N2 SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a silver halide'color photographic material, and more specifically to a silver halide multi-Iayered color photographic material according to thesubtractive process, each layer containing a mixture of at least two couplers that form a color image. The color photographic material of the invention isintendedto form'a large color gamut for low to high densities ofi the color image, and produces a color imagehaving high color purity.

2. Description of the Prior Art Many methods of producing color images by the subtractive process have previously been known, and a color photographicsystem consisting of a combination of a blue-sensitive layer (yellow producing), a greensensitive layer (magenta producing), and a redsensitive layer (cyan producing)-based on the principles of three primary colors is mainly in use today.

If an'object to be recorded as a color image is limited to those occurring in nature, there is no need to pay much attention to the size of a color reproducible gamut. However, synthetic dyes or pigments have recently comeinto widespread use, and there is an abundance of: colors-of high saturation in the environment of our daily lives. As a result, the object to be photographed frequently assumes a color of suchhigh saturation, and the color reproducible gamut of a colorimage needs to be considerably widened in order to faithfully reproduce these colors of high saturation.

It has now been found that the combination of colors which gives the largest color-reproducible color gamut depends' upon lightness, and with the conventional mul- 610 a 690 nm cyan magenta 5 l0 530 nm yellow 4l0 430 nm and when the maximum absorption wavelengths at the high density area are as follows cyan magenta 530 560 nm yellow In the accompanying drawings:

FIG. I is the (UN) chromaticity diagram of a color image;

FIG- 2 is a diagram illustrating the effects of thetheory described in detail in the specification;

FIG. 3 is a diagram showing the positions in the chromaticity diagram of FIG. 2 for a luminous transmittance (T) of 10 percent and percent;

FIG. 4 is a diagram illustrating the variations in the ratio of the amounts of dyes given by the competitive coupling between two couplers A and B; and

FIG. 5 gives diagrams each showing the realtion of the coupling actiiity of a coupler to the absorption of the resulting color image.

FIG. 1 shows the chromaticity diagram (U, V) obtained when dyes of the following peak wavelengths are used with a view to widening the gamut of a bright color cyan 700 mp magenta 53l my.

yellow 435 mg The trichromatic specification (X, Y, Z) is shown by the following:

(U. V) at this time are expressed as follows:

' "Z/= 4X/X+15Y+ 32) V=(6Y/X+ l5Y 3Z) When a mixed dye system having the following peak wavelengths cyan 640 mu magenta 543 my.

yellow 447 mp is used by applying the present invention to this color system, the color gamut is extremely widened.

InIthis case, the coupling rate of the first-mentioned color system is more than 1.5 times as great as that of the latter-mentioned color system. The rate of increase of the color' gamut so obtained is shown as follows for a luminous transmittance (T%) to 10 80 percent.

T(%). IO 20 40 80 Rate of increase( 7%) 44 27 I3 2 in FIG. 3 for a luminous transmittance (T) of percent and 80 percent.

The present invention is based on the abovedescribed theory, and intended to give a maximum color gamut corresponding to the variations in density of a color image by including two couplers differing in the rate of coupling in each layer of a photographic material, and causing them to develop colors selectively towards the high density area and the low density area.

SUMMARY OF THE INVENTION According to the present invention, there is provided a silver halide color photographic material comprising a support and a blue-sensitive silver halide emulsion layer containing a coupler which forms yellow upon coupling with an oxidation product of a color developer of the aromatic primary amine type, a greensensitive silver halide emulsion layer containing a coupler which forms magenta upon coupling with said oxidation product, and a red-sensitive silver halide emulsion layer containing a coupler which forms cyan upon coupling with said oxidation product on said support; characterized in that each of said couplers is colorless and has resistance to diffusion, and at least one of said emulsion layers contains at least two couplers of the following combinations:

1. in the case of the blue-sensitive silver halide emulsion layer,

the combination of coupler A having a high rate of coupling reaction and forming yellow with a maximum absorption wavelength within the range of 400 to 500 mu and coupler B having a lower rate of coupling reaction than coupler A and forming yellow having a maximum absorption wavelength at at least 5 mu longer than the maximum absorption wavelength of yellow formed by coupler A,

2. in the case of the green-sensitive silver halide emulsion layer,

the combination of coupler C having a high rate of coupling reaction and forming magenta with a maximum absorption wavelength within the range of 500 to 600 mp. and coupler D having a lower rate of coupling reaction than coupler C and forming magenta having a maximum absorption wavelength at at least 5 my. longer than the maximum absorption wavelength of magenta formed by coupler C,

3. in the case of the red-sensitive silver halide emulsion layer,

coupler E having a high rate of coupling reaction and forming cyan with a maximum absorption wavelength within the range of 600 to 730 mu and coupler F having a lower rate of coupling reaction than coupler E and forming cyan having a maximum absorption wavelength at at least 5 my. shorter than the maximum absorption wavelength of cyan formed by coupler E; the ratio of the coupling reaction rate of the firstmentioned coupler to that of the latter coupler in each of l to (3) above being at least 1.5 when measured in accordance with the method to be described hereinbelow.

Thus, the present invention is based on the fact that the shifting of the absorption of the color image is achieved by using two couplers differing in coupling activity conjointly within one emulsion layer.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Some of the prior art techniques of using different kinds of couplers in one emulsion layer will be briefly mentioned below. For example, US. Pat. No. 2,322,027 discloses a technique of preventing crystallization of couplers in an emulsion layer by using a mixture of different couplers having similar crystallinity. Japanese Patent Publication No. 391/1965 describes a technique of partially improving the incompleteness of the absorption characteristics of a color image obtained from a principal coupler by mixing a small amount of a coupler of different color with the principal coupler. For a special use, West German Pat. No. 1 ,O46,495 discloses that by using two couplers differing in the rate of coupling and giving images of different colors, for example, yellow and cyan, two color images of different colors and tones are obtained in superposed condition so as to render X-ray diagnosis easy.

The present invention differs from any of these conventional techniques in respect of mixing two couplers differing in the activity of coupling reaction and also slightly differing in the formation of color, the combination of the ratio of the coupling rates with the difference in absorption as defined below, and also in respect of the purpose of widening the color gamut of color photographic materials.

The present invention will be described below in greater detail.

The oxidation product of a color developer released from the silver halide particles being reduced by devel opment is coupled with a non-diffusing coupler incorporated in the emulsion particles. The rate of formation ofa dye at this time, it is known, is proportional to the product of the reaction rate constant multiplied by the effective density of the coupler. The non-diffusing coupler incorporated in the emulsion layer is consumed with the progress of formation of a dye. Incident to this, the effective density of the coupler is decreased, and the production of the dye will also be reduced proportionately.

It is thought that where two couplers are present as a mixture, each coupler takes the oxidation product of ,the developer according to the reaction rate constant and the effective density to give a dye.

With a view to illustrating the technique of the present invention quantitatively, the relation among factors for a system composed of two couplers A and B is shown below on the basis of a simplified model.

wherein R, and R are the reaction rate constants of couplers A and B respectively, F and F are the amounts of color formed by the couplers A and B respectively, and X, and X are the amounts of couplers A and B respectively that are utilized when a maximum formation of color is obtained by sufficient subjection of emulsions X and X to the developer oxidation product.

FIG. 4 shows the variations in the ratio of the amount of dyes given by the competitive coupling performed between two couplers when the ratio R IR of the couplers is one-third, one-half, l, 2, and 3.

When a photographic emulsion layer containing two non-diffusing couplers differing from each other in the activity of the coupling reaction and the absorption of the dye derived therefrom is exposed and then color developed, the absorption of the color image shifts from that of a dye derived from the coupler having a high coupling activity to that of a dye derived from the coupler having a lower coupling activity with an increase in the amount of silver developed. This is illustrated in FIG. 5. Couplers A and B, when added to an emulsion individually, exhibit the absorption shown in FIG. 5-1. The absorption obtained from a mixture of couplers A and B is shown in FIG. 5-3 when the coupling activity of coupler A is higher than that of coupler B and in F K]. 54 when it is lower than the latter. It is necessary for the realization of the present invention to use a coupler combination which will exhibit the shift of absorption of the type shown in FIG. 5-2 for yellow and magenta, and of the type shown in FIG. 5-4 for cyan.

For the preferred realization of the present invention, it is advantageous that two dyes to be derived from'the couplers to be mixed belong to the same absorption region, that is, a blue light region at 400 to 500 mp, a green light region at 500 to 600 mu, or a red light region'at 600 to 730 mg, and they differ from each other in absorption maximum by at least 5 mp.

Furthermore, for the preferred realization of the present invention, one of the couplers should have at least 1.5 times as great a coupling activity as the other.

Thus, for the preferred realization of the present invention, the combination of two couplers should be such that a specified relation inherent to the desired absorption region exits between the activity of the coupler reaction and the absorption of the resulting color images.

So long as this relation is satisfied, the two couplers can be chosen from non-diffusing coupling compounds y)-butylamidophenyl,

having a wide range of structures. Examples of especially useful couplers include acyl ace'tanilide compounds for formation of yellow; 5-pyrazolones; indazolones, and pyrazolobenzimidazoles for formation ofv magenta; and phenols and a-napthols for formation of cyan.

The yellow couplers used in the invention, that is, couplers A and B, can be chosen from compounds of a wide range of structures. Of these, acyl acetanilide 'compoun'dsgive especially good results. These compounds: are expressed by the following structural formula (l):

wherein R, is a tertiary alkyl group, unsubstituted or substituted cycloalkyl group, unsubstituted or substitutedaryl group, or unsubstituted or substituted bicycloalkyl group, R is an unsubstituted or substituted aryl group or heterocyclic group, and X is a hydrogen atom' or a group capable of being split off at the time of coupling.

In the general formula (I), examples of R, include tertiary alkyl groups having four to 32 carbon atoms such as t-butyl, 1,1-dimethylpropyl, l,ldibutylheptadecyl, l, l -diisobutylheptadecyl, or I ,l-di-tert.-butylheptadecyl unsubstituted cycloalkyl chloro-5-[a-(2,4-di-tert.-amylphenoxy) cylclohexyl, l-butylcyclohexyl, 2-ethylcyclohexyl, 3-

ethylcyclohexyl, l -ethoxycyclohexyl, lmethoxycyclohexyl, 2-butoxycyclohexyl, lmethoxyethyl cyclohexyl, 3-methoxymethyl cyclohexyl, l-phenylcyclohexyl, or l-toluylcyclohexyl group; unsubstituted bycycloalkyl groups such as a 7,7-dimethylnorbornyl group; bicycloalkyl groups substituted by a C C alkyl, alkoxy, alkoxyalkyl, or aryl group such as a 2-methyl-7,7dimethylnorbornyl, 2- octadecyl-7,7-dimethylnorbornyl, 2-ethoxy-7,7- dimethylnorbornyl, 2-octadekoxy-7,7-dimethylnorbornyl, 2-octoxydecyl-7,7-dimethylnorbornyl, or 2- phenyl-7,7-dimethylnorbornyl group; unsubstituted aryl groups such as a phenyl group; aryl groups substituted by a C -C alkyl group, alkoxy group, or alkoxyalkyl group, a halogen atom, amino group, carbonamide group, ureido group, sulfamyl group, sulfone group, or carboxyl group, such as a 3-methyl phenyl, 2-butyl phenyl, 4-dodecyl phenyl, 4-octadecyl phenyl, 2- trifluoromethyl phenyl, 2-methoxy phenyl, 2-butoxy phenyl, 2-octadekoxy phenyl, 4-methoxyethyl phenyl, 2-chlorophenyl, 2,4-dichlorophenyl, 4-aminophenyl,

4-N-methyl-N-butylamino phenyl, 2-N- propylamidophenyl, 3-butylamidophenyl, 2- octadec ylamidophenyl, 3-

octadecylsuccinomonoamidophenyl, 4-octadecylsuccinomonoamidophenyl, 3-a-(2,4-di-tert.-amylphenoxy-(4-N-butyl-N- pentadecyloxycarbonylamino) propionamidophenyl, 4-phenylureido, 4-toluylsulfamylphenyl, 3-sulfophenyl, or 3-carboxyphenyl group.

Examples of R include unsubstituted aryl groups such as a phenyl group; aryl groups substituted by a halogen atom, C -C alkyl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, amino group, carbonamide group, sulfonamide group, ureido group, carbamyl group, sulfamyl group, carboxyl group, or sulfo group, such as a 2-chlorophenyl, 2,4- dichlorophenyl, 2, 4, 6-trichlorophenyl, 2- bromophenyl, 2-fluorophenyl, 4 -methylphenyl, 4-trifluoromethylphenyl, 2 -methoxyphenyl, 4-[N-( 'yphenylpropyl)-N-(p-toluyl) carbamylmethoxy] phenyl,

2-phenoxyphenyl, 2 chloro-S-octanoylphenyl, 2- methoxy-S-octadecanoylphenyl, 2-methoxy-5- tetradecyloxycarbonylphenyl, 3,5-dimethoxycarbonylphenyl, 3,5-didodecyloxycarbonylphenyl, 2-chloro-5- [a-(2,4-di-tert.-amylphenoxy) acetamide] phenyl, 2-

butyramide] phenyl, 2-methoxy-5-['a-(2,4-di.-tert.-amylphenoxy) acetamide] phenyl, 2-chloro- 5-[y-(N-butyl-N-hexadecanoylamino)propionamide] phenyl, 3-octadecylsuccinomonoamidephenyl, 2-chloro-5-(4-methylphenylsulfonamide) phenyl, 4-phenylureidophenyl, 2- (2,4-di-tert.-amylphenoxy)-5-(3,5-dimethoxycarbonylphenylcarbamyl) phenyl, 3,5-dicarbamylphenyl, 4-[N- phenylethyl)-N-(p-toluyl)sulfamyl] phenyl, 4-

carboxyphenyl, 3,5-dicarboxyphenyl,' 2-methoxy-5- carboxyphenyl, 2-chloro-5-carboxyphenyl, 2- N- methyl-N-octylamino)-5-carboxyphenyl, 2-

pling, such as a halogen atom, a SCN group, OR, group, SR group, OCOR group, or OSO R group, where R, is an alkyl, aryl, or heterocyclic group. Examples of X include a fluorine, chlorine, bromine or iodine atom, an SCN group, phenoxy group, 4-nitro- 8 phenoxy group, acetyloxy group, 4 nitrophenyl-thio group, benzothiazolethio group, methylsulfonyloxy group, or 3nitrophenyl-sulfonyloxy group.

Examples of the diffusion-resistant yellow couplers 5 that can be used in the invention are as follows:

Coupler (1) 0 CH;

adhoQ-cocmoomzQ Con ler 2 CH: CraHu N I CHr0COCH:CONH- Coupler (3) C 00H C u l 4 o p at 01111350 ONE-Q 0 CH:

0 o omo ONE-Q cup Gino-Q0 OCHIC ONHQ NHCO CHCH=CHC1e al mo OOH 1 e Coup er CnHarCH=CHCH-C ONH-Q-C o omo ONE-Q H c 0 OH O 0 cm Coupler (7) C O OH C1eHa1CH=CHiH-CONH -oo CHlC ONH 0 OH H2O CH:

Coupler (8) v C 0 C H31 NHCOCH2CH;N

C4Ho

l cmQcocmoomrQ OCH;

(seawater; .LI

, 10 Continued Coupler (13) C 0 O CnHzr Coupler (14) (31115 1 (norm OCHCONH coomoomz-Q 5111101) 7 GHa Coupler (15) v /Ci lt( o0omooNH--s0m\' Cu M The above-eXemplifEd d iff usi ohaesistant yellow ureido group, sulfonamide group, or alkoxy group; R0

couplers of the, interior type can be synthesized by methods well known heretofore, such as those disclosed in detail in British Pat. 595,314, British Pat. 800,l08, British Pat. 1,045,633, British Pat. l,052,488, U.S .'Pat. No. 3,265,506, Belgian Pat.692,947, or Japanese Pat. application No. 3985/66.

The magenta couplers used in the invention, that is, couplers C and D, can be chosen from a wide range of compounds. Of these, 5-pyrazolone compounds give especiallygood results, which come within the structural formulae ll and jlll below.

7 (III) I is a lower alkyl group or aryl group; and X is a group that can be split off by the oxidation product of an aromatic primary amino compound as a developer, such as ahydrogen atom, halogen atom, cyano group, arylthio group, aryloxygroup, arylazo group, heteroazo group or acyloxy group. Useful substituents of the 'aryl group represented by R, are alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, trifluoromethyl, cyano, acyl, sulfonyl, acylamino, sulfonamino, ureido, amino, carboxyl, alkoxycarbonyl, and carbamyl groups and halogen atoms. Phenyl groups substituted by these substituents are especially preferred as R At least one of R and R contains a hydrophobic group having eight to 30 carbon atoms. The presence of the hydrophobic group leads to an increased affinity between couplers and between couplers and solvents for the couplers, and makes it possible to retain the coupler within or near the fine particles of a solvent for the coupler and thus render an intimate contact between them easy. The hydrophobic group also serves to impart affinity for the coupler solvent to the dye derived, and enhance the effectv of the coupler solvent. The hydrophobic group contained in R and/or R is bonded to the coupler residue' either directly or through two organic radicals having an amide linkage, ether linkage, ester-linkage, urea linkage, or sulfonamide linkage.

Specific examples of the S-pyrazolonc compounds which are used especially with satisfactory results are as follows:

Coupler (b) Specifically, the S-pyrazolone is dissolved in a coupler 5 solvent and the resulting solution is dispersed in an aqueous medium for photography. The use of a surface active agent such as those described in Japanese Patent No. 428,191 and Japanese Patent Application No.

60130/68 is useful at this time. In order to promote the 10 dissolving of the coupler in a solvent for the coupler, it is useful to use an organic solvent partially soluble in water and having a relatively low boiling point together with the coupler solvent. Examples of such auxiliary solvents include sec.-butyl alcohol, hexanol, cyclohexanol, ethyl acetate, butyl acetate, ethyl propionate, and tetrahydrofuran. I

According to an alternative method, an aqueous solution of the 5-pyrazolone coupler in an alkaline aqueous solution is added to a photographic emulsion in the presence of a dispersion of the coupler solvent which has a high boiling point, and then the mixture is neutralized. In this case, the use of a watermiscible organic solvent, such as methanol, ethanol, dioxane, dimethyl formamide, or dimethyl sulfoxide is useful for promoting the dissolving of the coupler in the aqueous medium. When the coupler is added to a photographic emulsion after having been made into its aqueous solution, 5-pyrazolone couplers of the structural formulae (ll) and (III) which have one carboxyl group in the molecule prove especially useful. The carboxyl group is present mainly in the form ofa free acid except when the coupler is added to the emulsion as an alkaline aqueous solution, and except when the-photographic material is treated with an alkaline developer solution, and it has affinity for the solvent. On account of this, the couplers vof this type and the dyes derived from them exhibit affinity to solvents for the couplers, which solvents are expressed by the structural formula MO E-F55 II; =0 N As a result, the combination of a coupler of this kind with the coupler solvent results in good color image absorption characteristics or reduced tendency of the coupler to crystallize. On the other hand, couplers having a strong acid group such as a sulfonic acid group or sulfoxylic acid group do not sufficiently exhibit effects ascribable to the coupler solvent.

Examples of the 5 -pyrazolone couplers having a carboxyl group which are suitable for adding as an aqueous solution to photographic emulsions in the presence of a dispersion of the coupler solvent of the structural formula N =0 0:!) N N N will be given below.

Coupler (y) /N=C- i1Ha5 M.P. 171l75 C.

0- H2 OOH Coupler (z) /N=CNHC O CHCH=OHC1H -N\ mo OOH 0011 let a p N=CNHCO- NHCOCH=CHC H C-CHz 1 33 g HzCOOH Coupler (b) Cl N=CNHCO C1 N HCO N CH=CHC H C CH2 N 38 1 H20 OOH Coupler (c) N=C-NHCO M P 196-199" C.

Q11. ll

As the magenta couplers are used in the invention, I group capable ofibeing split off by coupling reaction. that is,-couplers C andD,-indazolone compounds, py- "Couplers E and F should have a group capable of renrazolone benzimidazolercompounds and cyanoacetyl dering the coupler resistant to diffusion in order to fix coumarone compounds are also useful besides the the coupler within the emulsion'layer'with'outcrystalliabove-mentioned 5-pyrazolone couplers. Specific'ex- 5 zation.

amplesof these compounds are shown below. Examples of the cyan couplers are shown below.

CHEM-(I3 $112 M.P. 121-122 C.

M.P. above 250 C.

' nnoocmo- CsHn(t) .H 0 s oils-Germs) oNomo o-c l The cyan couplers ii afifi'msdih theinven tion ca n 1) 5 on be-chos'enfrom compounds ofa wide variety of structures. 0f these;compoundsexpressed by the general CONHCuHu formulae (lV) -and (V) -are' especially useful.

' Rio C ONHCnHu oor so g 1 X 3) Y on CONE-(CHflrQ-Cslinfi) NCOR1 5 5 511110) 3 R0 (V) (4) I OH 0 CONHCIBHU imhe-abo'veromnrae, eaenfafimaa R135 a hydro gen atom,.an alkyl group or a substituted alkyl group; s|o R; is an alkyl'group, substituted alkyl group, aryl group or substitutedlarylgroup; R is an alkyl group, substi- (5) OH tuted alkylgroup, aryl group, or substituted aryl group; i

each of Rgand R is ahydrogen atom, halogen atom, CONHCHICHINHCOCHCHHN lower alkyl group, or alkoxy group; and X is a hydrogen scan.

atom, halogenatom sulfone group, or other atom or 6 OH CH:

CON

CHICHZN CON CnHzs 2 (l; CH: B N) @conn-Q-ommmm CHgCHgCN CON OCiz zs CONHCHQ-OCuHu As the couplers E and F, phenol or alpha-naphthol compounds such as exemplified below can be similarly used besides the compounds of the generalformulae (IV) and (V).

lt is advantageous that the coupler used in the present invention has at least one hydrophobic group having eight to 35 carbon atoms within the molecule as a diffusion-resistance imparting group. This hydrophobic group serves to increase the cohesive force between molecules and promotes the formation of micelles or colloidal fine particles as a result of gathering of a number of coupler molecules. Since an assembly of these molecules cannot move within the polymer matrix that forms the emulsion layer, the coupler molecules are made resistant to diffusion.

The hydrophobic group that is useful in the present invention is selected from straight or branched-chain alkyl groups, alkenyl groups, aldoxyalkyl groups, alkoxyaryl groups, aryl groups, aryloxyalkyl groups, aryloxyaryl groups, and acylaminoalkyl groups. Specific examples of the hydrophobic group include the following:

1a zr-0 OCH2 lblsHBl Seer-05H --0 CH1- see-CaHn (viii) C 1H mwmmQ-o d11- l I t8It-C Hu (I N-CHzCHzn-C Hi;

Substituents are suitably selected in the above compounds so that the above-mentioned requirements for the realization of the present invention will be met. A useful means for achieving this object is to substitute a splittable atom or organic radical for the reaction site of the coupler because this changes the coupling reaction activity of the coupler without changing the absorption of the color image derived.

The spectral absorption of the color image is measured by a spectrophotometer. The wavelength corresponding tothe maximum value of the spectral absorption curve is called an absorption maximum wavelength and expressed by A The coupling reaction activity of the coupler can be determined as a relative value by measuring the amounts of two colors in the color images obtained by mixing two couplers A and B which give clearly separated different colors and adding the mixture to an emulsion, and then performing color development. If coupler A develops color of the maximum density (DA and color of density D in an intermediate stage, and coupler B develops colors of (D and D 21 respectively, theratio R /R of the reaction activities of both couplers is expressed by the following equation.

g of a'blue-"seiisitivephotographic emulsion containing 15.0 g of silver iodobromide containing 3.0 mole percent of iodide and 30.0 g of gelatin, and 20 ml. of a 3 percent acetone solution of triethylene phosphamide was added as a hardening agent. The resultant solution was coated on a cellulose triacetate film base to a dry DA Rn thickness of 6.5 microns. The photographic material log 1- (D obtained was designated as sample I.

In other words, the coupling activity ratio Rig/12,. caii In t e manner as Set forth above a Pi a be obtained fromthegradient of the straight line which graph: material (deslgnated. as Sample z f f l is obtained by plotting several sets of D and D '8 3 Coupler and P* 5g{] gl lcfmaterlla resulting from imparting several stages of exposure to (deslgnated as Sample] I) i g o coup er an emulsioncon'ta'ini'ng a mixed coupler and subjecting B alone were Prepared: h S 1 them to color'development, on two axes crossing at Plmtogmph1c Processmg of Each 6 amp es n l a hvt as f g f A isaeir aiiei'ai ai ssuies' was giverfto sash 5i PY? l1YF:9'Tr colup I the samples for sensitometry, and the sample was dethe required relations 1p etween e co or mage a veloped by the following procedum sorptlon and the coupling aCllVltleS are mixed w th each other so that one component is from to 80 mole percent of the entire mixture. The mixing ratio is 20 i V to be controlled properlyaccording to the purpose of O T 1 T using the color photographic material, the difference in (m'nums) color image absorption between the two couplers, and go the coupling-activity ratio. gf 'g g Z The invention willfurther be described by the follow- First fixati go. 3:

. s. 1 v Rinsing mg non llmltatlve Examples. Bleaching g g Ri n v 0.

EXAMPLE 1 502:1? fixation. dob 2g 1. Couplers Used in thePresent Example Rmsmg Coupler'A....;. g /CH3 M.P.125

I SOzN V J: ClsHal 430 Hc0NH- I CH: CHI

Coupler Cal-Is M-P- 92-93 C- Nnooenooimim CH3 om-e-ooomoomioiHiiu Ha I " The above couplersii aiiii ii 'eesidi'images-1150115,; a maximum absorption wavelength of 439 my. and 450 developer mp. respectively 'whenusing N, N-diethyl-3-methyl-4- water I 000 aminoariiline as a developer and trihexyl phosphate as Ben zyl alcohol 12.0 m I a coupler solvent. When'they were caused to develop 2232::.ij ifl'sa zfgmif colors competitively using as a standard coupler 5 Sodiumuflaonule(mon0i1ydralc) 2715:: methyl 4,6 dichlol'o-2-[-(2';4' di-t-amylphen0xy)- z f zf g fg'f z f fglz l5 sacetarnide]phenol,the relative values of the coupling (B h lf z id qi fli reaction speed constants obtained were 2.84 and 0.20 Sesquisulfme (monohydwlct slf- Fixing solution g ll=4.5 2. Preparation of Photographic Materials w t l 000 I I :1 er m A mixture consisting of 3.4 g of coupler A, 2.9 g of Sodium ,hiosumne hmhydmc 80 g coupler B, 10 ml. of dl-n-butyl phthalate, and 30 ml. of Sudium sulfile anllydiidv. 5 gethyl acetate was heated to C. The resulting solution mic acid 25 was mixed with 150 g'of a 10 percent gelatin aqueous 60 POluSh alum 7 g. solution'containirlg'0.4 g of sodium dodecylbenzenesul- Bl go caching solution {pH-7.2) fonate held at 50 C., and the mixture was vlgorously stirred mechanicallywith a high speed mixer to make an Red prusslute 17 g. i l i l l d ll dd d 500 gm OI'IC ilCl e resu tant coup er lsperslon was a a e to Potassium bromide 7 g- Table 1 Absorption maximum wavelength (m t) Samples Couplers Maximum absorbance of color images l A B 437 439 442 444 ll A 435 436 435 435 III B 446 447 448 447 The results given in Table 1 demonstrate that the selected combination of couplers A and B gives a yellow color image in which the maximum absorption wavelength shifts to the longer wavelength side with an increase in color formation, which wavelength shift is g of gelatin and 15.0 g of silver iodobromide containing 3.0 mole percent of iodide. The pH of the solution was adjusted to 7.0 with a 4 percent sodium hydroxide solution, and then 20 ml. of a 3 percent acetone solution of triethylene phosphamide was added as a hardening agent. The resulting solution was coated on a cellulose triacetate film to a thickness of 4 microns. The resulting photographic material was designated as sample IV.

Using 6.0 g of coupler C alone, sample V was similarly produced, and using 7.0 g of coupler D, sample VI was similarly produced.

3. Photographic Processing of Each of the Samples A graded series of exposures was given to each of the samples for sensitometry, and the same procedure was repeated as in Example 1 except that each sample was treated for 10 minutes at 21C. using the developer solution (ll) of the following formulation.

Color developer ll (pH=l0.5)

suitable for widening the color reproduction gamut of Water I i 1.000 ml.

1 fl S Z-Amtno-S-drethylammoc0 or l m 25 toluene hydrochloride 2,5 Sodium sulfitc anhydride 5 3. EXAMPLE 2 Sodium carbonate monohydrate 47 g. Potassium bromide 2 l. Couplers Used in this Example Coupler C M.P. 140-142" C.

NHCOCHzO- CrCMsee) /N=CNHC 0Q 5H11(380) @K C- H: l

C u l 1' D M.P. 141 0.

N NHCOCH-O canteen Cl 2H:

/N=CNHC O sHuGert) Cl N\ C-CH;

hexyl phosphate, ml. of ethyl acetate and 0.5 g of sodium ot-sulfo-di-t-octylsuccinate were heated to 60C.

The resultant solution was admixed with 100 ml. of a l0 percent gelatin solution containing 1.0 g of citric acid and held at C., and the mixture was passed through a colloid mill ten times to obtain a dispersion with fine emulsification.

The entire coupler dispersion was added to 500 g of a green-sensitive photographic emulsion containing 30 4.. Measurement of Spectral Absorption and Conclusion The spectral absorption of the color image was measured as to each of the samples. As a result, the following absorption maximum wavelengths were obtained.

Table 2 Absorption maximum wavelengths (mg) m Couplers Maximum absorbance of color images IV c D 538 540 542 543 v c 536 537 537 531 VI D 547 548 547 548 The results given in Table 2 demonstrate that the selected combination of couplers C and D achieves a wavelength shift suitable for widening the color reproduction gamut of color films as a result of the shifting of the maximum absorption wavelength to the longer wavelength side with an increase in color formation.

EXAMPLE 3 1. Couplers Used in the Pr esent Example The results given in Table 3 demonstrate that the selected combination of couplers E and F gives a cyan color image in which the maximum absorption wave- Coupler E M.P. above 250 C.

When N.N-diethyl-3 methyI-4-aminOani1ine was used as a color developer, coupler E showed a'maximum absorption at 707 my, and coupler F dispersed in di-n-butylphthalate shows a maximum absorption at 64 11: T at ys cou l n Speed o s measured using a-benzoy1-aceto-(2-methoxy -carbonyl-ndodecyloxy) anilide as a standard coupler was 1.60 for coupler E, and 0.65 for coupler F. I

2. Preparation of Photographic Materials Coupler E (1.63 g), 3.0 ml. of di-n-butyl phthalate, andv ml. of ethyl acetate were heated to 60C. The resultant solution was admixed with 50 ml. of a 8 percent aqueous solution of gelatin containing 0.2 g of sodium cetylsulfate, and finely emulsified by giving a vigorous mechanical stirring using a homoblender.

The resulting coupler dispersion was added to 300 g of a red-sensitive photographic emulsion containing 12 g of gelatin and 7.5g of silver iodobromide containing 5.2 molepercent of iodide, and then 100 ml. of an alkaline aqueous solution containing 3.5 g of coupler E.

. The pH of the solution was adjusted to 7.0 with 5 percent acetic acid. Then, ml. of a 3 percent acetone solution of triethylene phosphamidewas added as a hardening agent. The resultant solution was coated on a cellulose triacetate film to a thickness of 4 microns. The resulting photographic material was designated as sample V11.

By the same procedure, sample Vlll was prepared using 5.4 g of coupler E alone, andsample lX was prepared using 4.9 g of coupler F alone. 3. Photographic Processing of Each of the Samples A graded series of exposures was given to each of the samples for sensitometry, and the samples were developed in the same way as set forth in Example 2. 4. Measurement of Spectral Absorption Characteristics The spectral absorption characteristics of the magenta, color obtained as a result of thedevelopment were measured.

As shown in Table 3, the absorption maximum wavelengthsof the color images of these samples showed. dependence upon maximum absorbance.

Table 3 Absorption maximum wavelengths (mp) length shifts to the shorter wavelength side with an increase in color formation, which wavelength shift is suitable for widening the color reproduction gamut of color films.

EXAMPLE 4 taining 2,5 -dioctylhydroquinone was coated on top of the second layer in a dry thickness of 1 micron. On top of it, the same green-sensitive emulsion containing a mixture of couplers C and D as used in Example 2 was Operation Temperature (C.) Time (minutes) First development. 2| 12 Stop bath do. 2 Rinsing do. 3

Uniform exposure (500 W tungsten lamp. 30 cm, 2 minutes) Color development 10 Rinsing do. 1 Fixation do. 4 Rinsing do. 3 Bleaching do. 3 Rinsing do. 2 Fixation do. 3

Rinsing.

For the color development, the above-mentioned color developer solution I was used. The fixation solution and the bleaching solution used were of the formulations'described in Example 1. As the stop bath, a 1.5

percent aqueous solution of acetic acid was used.

A solution of the following formulation was used for t e firs svs pmsnt Water 1.000 ml. N-mcthyluminophcnol sulfate 3.5 g. Sodium sulfitc (unhydridc) 40 g. Hydroquinonc 7.0 g. Sodium carbonate monohydrute 40 g. Sodium thiocyanate 2.0 g Potassium bromide 20 g Potassium iodide 0.0l g

taining coupler D, and a blue-sensitive emulsion layer containing coupler B. Each of the samples was exposed, and processed in the same way as set forth above.

The color reproduction gamut of colors obtained by these three film samples was determined. Sample (XI) of the conventional combination has a color reproduction region shown by a solid line in FIG. 1 and Sample (X) of the present invention has a color reproduction region shown in FIG. 3. The shift of the range of FIG. 1 from FIG. 3 is indicated by a dotted line in FIG. 3. It will-be understood from FIG. 3 that the same result was obtained in a comparison of sample (X) and old sample (XII). As a result, sample (X) of the present invention gives a wavelength shift which is proper for widening the color ie r'o'duaiori'fgidhdfbokir films with an in crease in color formation.

when using N,N-diethyl-3-methyl-4-aminoaniline as a color developer and .tri-n-hexyl phosphate as a coupler solvent. When they were caused to develop colors competitively using as a standard coupler 5-methyl-4,6- dichloro-2-[2',4-di-t-amylphenoxy) acetamide] phenol, the relative values of the coupling reaction speed constants obtained were 0.75 for coupler C and 0.05 for coupler D.

Coupler C (3.5 g), 2.2 g of coupler D, 17 ml. of trin-hexyl phosphate, 30 ml. of ethyl acetate and 0.4 g of sodium a-sulfodi-(Z-ethylhexyl) succinate, were heated to 60C. The resultant solution was admixed with 70 ml. of a 10 percent aqueous solution of gelatin containing 0.5 g of citric acid and held at 50C., and by passing the mixture through a small-sized colloid mill IO times, a finely emulsified dispersion was obtained.

The entire coupler dispersion so obtained was added to 300 g of a green-sensitive emulsion containing 20.0 g of silver chlorobromide and 25 g of gelatin, and the pH of the mixture was adjusted to 6.5 with a 4 percent sodium hydroxide solution. With the addition of 10 ml.

of a 3 percent acetone solution of triethylene phosphamide as a hardening agent, a magenta-forming composition was prepared.

On photographic baryta paper were coated a bluesensitive emulsion containing coupler A' shown below in a dry thickness of 5 microns, an aqueous gelatin solution in a dry thickness of 1.5 microns, and the above magenta-forming composition as a third layer in a dry thickness of 4 microns one on top of the other in this order. Furthermore, on top of the .third layer was coated a gelatin layer containing 2-benzotriazolyl-4,6- di-t-aminophenol in a dry thickness of 1.5 microns, and as a fifth layer, a red-sensitive emulsion layer containing 5-methyl-4,6-dichloro-2-[(2',4-di-t-amylphenoxy) acetamide] phenol in a dry thickness of 3 microns. As

EXAMPLE 5 a topmost layer, an aqueous gelatin solution was ap- Gdupler o'- 0111f '7 i nirja'u s o.

NHomOQmHHm 01 I:

/N=CNHC 0 Hit (0 011,0 N\

Coupler D N=C--C11Hu M.P. 144-146" 0.

1 H N H Couplers C and D give a color image having an absorption maximum of 544 my. and 562 mp. respectively plied in a thickness of 1 micron thereby to produce color photographic paper.

Coupler A cmo-Qooomoomz The magenta color image obtained by green light 30 Superior color reproducibility equivalent to sample X was obtained. Each of the layers of this film showed the following absorption maximum wavelengths.

Table 5 showed the following absorption dependent on light- 5 Absorption maximum wavelength (mu) T bl 4 Color hue Coupler Maximum absorbuncc of color image L 1.5 2.0 Absorption maximum wavelength (mu) Maximum 'absorbance (reflectance) of color image 10 22222 5 L0 "5 20 Cyan E F 685 672 669 665 540 545 551 553 a. j a a a V I These absorption maximum wavelengths showed de- EXAMPLE 6 pendence on lightness as mentioned before. Color slid- Coupler E'- 0H 235-236 C.

' (decomposition).

CONHCHgCHzNHCOfiJH-QsHaa Coupler F OH M.P. 150 0.

C1 NHCOCHO- C5Ht1(t).

CH; CaHMt) When "N, N diethyl-Ii-methyl-4-aminoaniline was used as acolor developer, coupler E exhibited a maximum absorption at 710 mu, and coupler F dissolved in-di-n-butylphthalate, at 658 mu. The relative coupling. speed constant measured using a-(omethylbenzoyl)-aceto-( 2-methoxy-5-carbonyl-nacetoxy) anilide as a standard coupler was 4.0 for coupler E. and 0,9 forcoupler F.

A solution obtained by heating 2.5 g of coupler F, 4 ml. of di-n-butyl phthalate, and 3 ml. of ethyl acetate to 60C. was admixed with 40 ml. of an 8 percent aqueous gelatin solution contain ingpl g of sodium cetylsulfate, and the mixture was stirred vigorously with a homoblender to emulsify them finely.

The coupler dispersion obtained above was added to 450g of a red-sensitive emulsion containing 1 l g of, silver iodobromide and 18 g of gelatin, and then a solu. tion of-2.9 g of coupler E in-70 ml. of water containing 10 ml. of a'4'percent aqueous solution of sodium hydroxide was added. The pH of the mixed solution was then adjusted to 7.0 with 5 percent acetic acid. Then, as a hardening agent, 12 ml. of a 3 percent aqueous solution of dichlorooxy-S-triazine-sodium was added to prepare a cyan-forming composition.

A multi-layer coated'film was produced in the same way as set forth above in Example 4 except that the above cyan-forming composition was coated as a second layer in a dry thickness of 4.5 mt.

The resultant film-was exposed, and then subjected to the reversal color development in the same way as setforth in Example 4 except that color developer solution ll] of the following formulation was used as color developer solution.

Color developer solution I" N,N'-diethyl-p-phenylcnediaminc sulfate es obtained from, this film reproduced a wide range of colors.

What is claimed is:

1. A silver halide color'photographic multilayer material comprising a support, a blue-sensitive silver halide emulsion layer containing a coupler which forms a yellow dye upon coupling with an oxidation product of a color developer of the aromatic primary amine type, a green-sensitive silver halide emulsion layer containing a coupler which forms a magenta dye upon coupling with said oxidation product, and a red-sensitive silver halide emulsion layer containing a coupler which forms a cyan dye upon coupling with said oxidation production; each of said layers being on said support; wherein each of said couplers is normally colorless prior to exposure and development-and is substantially nondiffusing; and v v wherein at least one of said emulsion layers contains at least two couplers of the following combinations:

1. in the case of said blue-sensitive silver halide emulsion layer, the combination of a first couplerltaving a high rate of coupling reaction and forming a yellow dye with a maximum absorption wavelength within the range of 400 to 500 my. and a second coupler having alower rate of coupling reaction than said first coupler and. forming a yellow dye having a maximum absorption wavelength at least 5 mp. longer than the maximum absorption wavelength of the yellow dye formed by said first coupler,

2. in the case of said green-sensitivesilver halide emulsion layer, the combination of a third coupler having a high rate of coupling reaction and forming a magenta dye with a maximum absorption wavelength within the range of 500 to 600 my. and a fourth coupler having a lower rate of coupling reaction than said third coupler and forming a magenta dye having a maximum absorption wavelength at least 5 mp. longer than the maximum absorption wavelength of the magenta dye formed by coupler C,

3. in the case of the red-sensitive silver halide emulsion layer, the combination of a fifth coupler having a high rate of coupling reaction and forming a cyan dye with a maximum absorption wavelength within the range of 600 to 730 my and a sixth coupler having a lower rate of coupling reaction than said fifth coupler and forming a cyan dye having a maximum absorption wavelength at at least mp. shorter than the maximum absorption wavelength of the cyan dye formed by said fifth coupler; and

wherein the ratio of the coupling reaction rates of said first coupler to said second coupler, of said third coupler to said fourth coupler, and of said fifth coupler to said sixth coupler is at least 1.5, the coupling reaction rate of said couplers being shown by the expression:

wherein D represents the density of the color formed at an intermediate stage prior to full development and D,,,,,, represents the maximum color density achieved by full development of said couplers.

2. The photographic material of claim 1 wherein said first and second couplers are selected from acylacetanilide compounds of the formula:

, wherein R is a. a tertiary alkyl group having from four to 32 carbon atoms, b. an unsubstituted or substituted cycloalkyl group substituted by a C, C carbon containing alkyl, alkoxy, alkoxyalkyl, or aryl group, .c. an unsubstituted or substituted aryl group substituted by a C C carbon containing alkyl, alkoxy, or alkoxyalkyl group, a halogen atom, or an amino, carbonamide, ureido, sulfamyl, sulfone or carboxyl group, d. an unsubstituted or substituted bicycloalkyl group substituted by a C, C carbon containing alkyl, alkoxy, alkoxyalkyl or aryl group; wherein R is a. an unsubstituted or substituted aryl group substituted by halogen or by a C,- C carbon containing alkyl, alkoxy, aryloxy, aryl alkoxycarbonyl, amino, carbonamide, sulfonamide, ureido, carbamyl, sulfamyl carboxyl or sulfo group; or

b. a heterocyclic group; and X is a hydrogen atom or a group capable of being split off at the time of coupling.

3. The photographic material of claim 2, wherein said R is selected from the group consisting of a tertiary (C -C alkyl group; a substituted or unsubstituted cycloalkyl group, wherein the substituent is a (C -C alkyl. alkoxy. alkoxyalkyl or aryl group; a substituted or unsubstituted bicycloalkyl group wherein the substituent is selected from the group consisting of a C ,C alkyl, alkoxy, alkoxyalkyl and aryl group; and a substituted or unsubstituted aryl group, wherein the substituent is selected from the group consisting of a (C -C alkyl, alkoxy or alkoxy-alkyl group, a halogen atom, an amino group, a carbonamide group, a ureido group, a sulfamyl group, a sulfone group and a carboxyl group; said R is an aryl group, a substituted aryl group,

wherein the substituent is a halogen atom, an amino group, a carbonamide group, a sulfonamide group, a ureido group, a carbamyl group, a sulfamyl group, a carboxyl group, a sulfo group or a C -C alkyl, alkoxy, aryloxy, acyl or alkoxy-carbonyl group, or a heterocyclic group selected from the group consisting of 2- thiazole and 2-benzothiazole; and said X is a hydrogen atom or a group capable of being split off at the time of coupling selected from the'group consisting of a halogen atom, -SCN, OR SR -OCOR and -OSO R wherein R is an alkyl, aryl or heterocyclic group.

4. The photographic material of claim 1 wherein said third and fourth couplers are selected from 5- pyrazolone compounds of the formulae:

and

wherein R is an unsubstituted or substituted aryl group substituted by an alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, trifuoromethyl, cyano, acyl, sulfonyl, acylamino, sulfonamino, ureido, amino, carboxyl, alkoxycarbonyl, carbamyl group or a halogen atom;

wherein R is a alkyl group, an alkenyl group, an aryl group, a substituted aryl group substituted by an alkoxy group, an amino group, a substituted amino group substituted by an aryl group, an acylamino group, a substituted ureido group substituted by an alkyl or aryl group, a sulfonamide group, or an alk- Y 'Q P; H

wherein R is a lower alkyl group or an aryl group;

and

X is a group capable of being split off by an oxidation product of an aromatic primary amino compound used as a developer; and at least one of R and R contains a hydrophobic group having from 8 to 30 carbon atoms.

5. The photographic material of claim I, wherein said third and fourth couplers are selected from the group consisting of indazolone compounds, pyrazolobenzimidazole compounds and cyanoacetyl coumarone compounds.

6. The photographic material of claim 1 wherein said fifth and sixth couplers are selected from compounds of the following formulae:

wherein R is hydrogen, an alkyl group or an aryl group,

wherein R is an alkyl group, an aryloxy substituted alkyl group, or an aryl group; 7

wherein R and R each is a hydrogen or halogen atom, or a lower alkyl group, or an alkoxy group;

third and fourth couplers'are selected from pyrazolone compounds of the formulae:

and

l l R4 4 wherei'ifii} is an unsabsfitarezrat subst iiuted aryl group substituted by an alkyl, aryl, alkoxy, aryloxy, alkylthio,

'arylthio, trifuoromethyl, cyano, acyl, sulfonyl, acylamino, sulfonamino, ureido, amino, carboxyl, alkoxycarbonyl, carbamyl group or a halogen atom; I

wherein R is an alkyl group, an alkenyl group, an aryl group, a substituted aryl group substituted by an alkoxy group, an amino group, a substituted amino group substituted by an aryl group, an my]- amino group, a substituted ureido group substituted by an alkyl or aryl group, a sulfonamide group, or an alkoxy group;

wherein R is a lower alkyl group or an aryl group; and X is a group capable of being split off by an ox idation product of an aromatic primary amino compound used as a developer; and at least one of R and R contains a hydrophobic group having from eight to 30 carbon atoms, and

wherein, in said red sensitive silver halide emulsion layer said fifth and sixth couplers are selected from compounds of the following formulae:

| N-GO B1 and wherein R is h dragefi; an alkyhgroup or an aryl group,

wherein R is an alkyl group, an arloxy substituted alkyl group, or an aryl group;

wherein R and R each is a hydrogen or halogen atom, or a lower alkyl group, or an alkoxy group;

wherein R and R each is a hydrogen atom or a substituted alkyl group substituted by an acylamino group, a cyano group, or an aryl group, or a substituted aryl group substituted by an alkyl carbamoyl or alkoxy group, and X is an atom or group capable of being split off by the coupling reaction.

8. The photographic material of claim 1 wherein, in said green-sensitive silver halide emulsion layer, said third and fourth couplers are selected from the group consisting of indazolone compounds, pyrazolobenzimidazole compounds and cyanocetyl coumarone compounds,

wherein, in said red-sensitive silver halide emulsion layer, said fifth and sixth couplers are selected from compounds of the following formulae:

N-COR1 R 1 and 1 R o CON\. i Rn atom, or a lower alkyl group, or an alkoxy group;

wherein R and R each is a hydrogen atom or a substituted alkyl group substituted by an acylamino group, a cyano group, or an aryl group, or a substituted aryl group substituted by an alkyl carbamoyl or alkoxy group, and X is an atom or group capable of being split off by the coupling reaction.

9. The photographic material of claim 1, wherein said fifth and sixth -couplers are selected from the group consisting of phenols and a-naphthols.

10. The photographic material of claim 1, wherein said third and fourth couplers are selected from the group consisting of S-pyrazolones, indazolones and pyrazolobenzimidazoles.

11. The photographic material of claim 1, wherein said first and second couplers are selected from acyl acetanilide compounds.

12. The photographic material of claim 1 wherein, in said green-sensitive silver halide emulsion layer, said third and fourth coupler are selected from the group consisting of S-pyr'azolones, indazolones and pyrazolobenzimidazoles, and in said red-sensitive silver halide emulsion layer, said fifth and sixth couplers are selected from the group consisting of phenols and -naph thols. 

2. The photographic material of claim 1 wherein said first and second couplers are selected from acylacetanilide compounds of the formula:
 2. in the case of said green-sensitive silver halide emulsion layer, the combination of a third coupler having a high rate of coupling reaction and forming a magenta dye with a maximum absorption wavelength within the range of 500 to 600 m Mu and a fourth coupler having a lower rate of coupling reaction than said third coupler and forming a magenta dye having a maximum absorption wavelength at least 5 m Mu longer than the maximum absorption wavelength of the magenta dye formed by coupler C,
 3. in the case of the red-sensitive silver halide emulsion layer, the combination of a fifth coupler having a high rate of coupling reaction and forming a cyan dye with a maximum absorption wavelength within the range of 600 to 730 m Mu and a sixth coupler having a lower rate of coupling reaction than said fifth coupler and forming a cyan dye having a maximum absorption wavelength at at least 5 m Mu shorter than the maximum absorption wavelength of the cyan dye formed by said fifth coupler; and wherein the ratio of the coupling reaction rates of said first coupler to said second coupler, of said third coupler to said fourth coupler, and of said fifth coupler to said sixth coupler is at least 1.5, the coupling reaction rate of said couplers being shown by the expression: log (1-D/Dmax) wherein D represents the density of the color formed at an intermediate stage prior to full development and Dmax represents the maximum color density achieved by full development of said couplers.
 3. The photographic material of claim 2, wherein said R1 is selected from the group consisting of a tertiary (C4-C32) alkyl group; a substituted or unsubstituted cycloalkyl group, wherein the substituent is a (C1-C18) alkyl, alkoxy, alkoxyalkyl or aryl group; a substituted or unsubstituted bicycloalkyl group wherein the substituent is selected from the group consisting of a (C1-C18) alkyl, alkoxy, alkoxyalkyl and aryl group; and a substituted or unsubstituted aryl group, wherein the substituent is selected from the group consisting of a (C1-C18) alkyl, alkoxy or alkoxy-alkyl group, a halogen atom, an amino group, a carbonamide group, a ureido group, a sulfamyl group, a sulfone group and a carboxyl group; said R2 is an aryl group, a substituted aryl group, wherein the substituent is a halogen atom, an amino group, a carbonamide group, a sulfonamide group, a ureido group, a carbamyl group, a sulfamyl group, a carboxyl group, a sulfo group or a C1-C18 alkyl, alkoxy, aryloxy, acyl or alkoxy-carbonyl group, or a heterocyclic group selected from the group consisting of 2-thiazole and 2-benzothiazole; and said X is a hydrogen atom or a group capable of being split off at the time of coupling selected from the group consisting of a halogen atom, -SCN, -OR3, -SR3, -OCOR3 and -OSO2R3 wherein R3 is an alkyl, aryl or heterocyclic group.
 4. The photographic material of claim 1 wherein said third and fourth couplers are selected from 5-pyrazolone compounds of the formulae:
 5. The photographic material of claim 1, wherein said third and fourth couplers are selected from the group consisting of indazolone compounds, pyrazolobenzimidazole compounds and cyanoacetyl coumarone compounds.
 6. The photographic material of claim 1 wherein said fifth and sixth couplers are selected from compounds of the following formulae:
 7. The photographic material of claim 1 wherein in said green-sensitive silver halide emulsion layer said third and fourth couplers are selected from 5-pyrazolone compounds of the formulae:
 8. The photographic material of claim 1 wherein, in said green-sensitive silver halide emulsion layer, said third and fourth couplers are selected from the group consisting of indazolone compounds, pyrazolo-benzimidazole compounds and cyanocetyl coumarone compounds, wherein, in said red-sensitive silver halide emulsion layer, said fifth and sixth couplers are selected from compounds of the following formulae:
 9. The photographic material of claim 1, wherein said fifth and sixth couplers are selected from the group consisting of phenols and Alpha -naphthols.
 10. The photographic material of claim 1, wherein said third and fourth couplers are selected from the group consisting of 5-pyrazolones, indazolones and pyrazolobenzimidazoles.
 11. The photographic material of claim 1, wherein said first and second couplers are selected from acyl acetanilide compounds.
 12. The photographic material of claim 1 wherein, in said green-sensitive silver halide emulsion layer, said third and fourth coupler are selected from the group consisting of 5-pyrazolones, indazolones and pyrazolobenzimidazoles, and in said red-sensitive silver halide emulsion layer, said fifth and sixth couplers are selected from the group consisting of phenols and -naphthols. 